Electrocatalyst for electrochemical conversion of carbon dioxide

ABSTRACT

The electrocatalyst for the electrochemical conversion of carbon dioxide includes a copper material supported on titania nanotubes. The copper material may be pure copper, copper and ruthenium, or copper and iron supported on the titania nanotubes. The electrocatalyst is prepared by first dissolving copper nitrate trihydrate in deionized water to form a salt solution. Titania nanotubes are then added to the salt solution to form a suspension, which is then heated. A urea solution is added to the suspension to form the electrocatalyst in solution. The electrocatalyst is then removed from the solution. In addition to dissolving the copper nitrate trihydrate in the volume of deionized water, either iron nitrate to monohydrate or ruthenium chloride may also be dissolved in the deionized water to form the salt solution.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to electrochemical catalysts, andparticularly to AN electrocatalyst for the electrochemical conversion ofcarbon dioxide to hydrocarbons.

2. Description of the Related Art

Over the past several decades, various electrode materials have beenresearched for the reduction of carbon dioxide (CO₂) into differentproducts, most notably formic acid, carbon monoxide (CO), methane andmethanol. Conventional metals used in the research were provided in theform of high purity foils, plates, rotating discs, wires, beds ofparticles, tubes and mesh. These are all macroscopic materials, thus,when compared to microscopic or nanoscopic materials, they all haverelatively low surface areas and low conductivity electrical supports.

It would be desirable to provide an electrocatalytic material formed onnanostructures, thus greatly increasing available reactive surface areaand conductivity. Given the destructive nature of carbon dioxide as agreenhouse gas, increasing efficiency of eleetrocatalysts to form benignhydrocarbons, such as methanol, is obviously quite important. Further,it would be desirable to not only increase the overall efficiency of thecatalytic process, but also provide an electrocatlayst that operatesunder relatively low temperatures and in the range of atmosphericpressure.

Thus, an electrocatalyst for the electrochemical conversion of carbondioxide solving the aforementioned problems is desired.

SUMMARY OF THE INVENTION

The electrocatalyst for the electrochemical conversion of carbon dioxideincludes a copper material supported on titania nanotubes. The coppermaterial may be pure copper, such that the pure copper forms 20 wt % ofthe electrocatalyst; OR copper and ruthenium supported on the titaniananotubes such that the copper forms 20 wt % of the electrocatalyst andthe ruthenium forms 20 wt % of the electrocatalyst; or copper and ironsupported on the titania nanotubes such that the copper forms 20 wt % ofthe electrocatalyst and the iron forms 20 wt % of the electrocatalyst.The metal supported on titania nanotubes is prepared using homogenousdeposition-precipitation with urea.

The electrocatalyst is prepared by first dissolving copper nitratetrihydrate (Cu(NO₃)₂3H₂O) in deionized water to form a salt solution.Titania nanotubes are then added to the salt solution to form asuspension, which is then heated. A urea solution is added to thesuspension to form the electrocatalyst in solution. The electrocatalystis then removed from the solution. In addition to dissolving the coppernitrate trihydrate (Cu(NO₃)₂3H₂O) in the deionized water, either ironnitrate monohydrate (Fe(NO₃)₂H₂O) or ruthenium chloride (RuCl₃) may alsobe dissolved in the deionized water to form the salt solution.

These and other features of the present invention will become readilyapparent upon further review of the following specification.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The electrocatalyst for the electrochemical conversion of carbon dioxideincludes a copper material supported on titania nanotubes. The coppermaterial may be pure copper, such that the pure copper forms 20 wt % ofthe electrocatalyst; or copper and ruthenium supported on the titaniananotubes such that the copper forms 20 wt % of the electrocatalyst andthe ruthenium forms 20 wt % of the electrocatalyst; or copper and ironsupported on the titania nanotubes such that the copper forms 20 wt % ofthe electrocatalyst and the iron forms 20 wt % of the electrocatalyst.

The electrocatalyst is prepared by first dissolving copper nitratetrihydrate (Cu(NO₃)₂3H₂O) in deionized water to form a salt solution.Using exemplary quantities, the copper nitrate trihydrate is dissolvedin approximately 220 mL of the deionized water and then stirred forapproximately thirty minutes. Using the exemplary volume of deionizedwater given above, approximately one gram of titania nanotubes of 2-4 nmdiameter are then added to the salt solution to form a suspension, whichis then sonicated for approximately one hour and heated to a temperatureof approximately 90° C. with stirring.

A urea solution is added to the suspension to form the electrocatalystin solution. Using the exemplary quantities given above, approximately30 mL of an approximately 0.42 M aqueous urea solution may be added tothe suspension. Preferably, the urea solution is added to the suspensionin a drop-wise fashion. The urea solution and suspension are thenmaintained at a temperature of approximately 90° C. for approximatelyeight hours, with stirring.

The electrocatalyst is then removed from the solution, preferably byfirst cooling the solution to room temperature, centrifuging thesolution to separate out the electrocatalyst, and then washing anddrying the catalyst at a temperature of approximately 110° C. overnight.The electrocatalyst may then be calcined at a temperature ofapproximately 450° C. for approximately four hours in an argon gas flow.Following calcination, the electrocatalyst is reduced at a rate ofapproximately 100 mL/min at a temperature of approximately 450° C. forapproximately four hours in a gas flow of approximately 10% hydrogen inargon.

In addition to dissolving the copper nitrate trihydrate (Cu(NO₃)₂3H₂O)in the deionized water, either iron nitrate monohydrate (Fe(NO₃)₂H₂O) orruthenium chloride (RuCl₃) may also be dissolved in the deionized waterto form the salt solution.

The titania nanotubes preferably have diameters of approximately 2-4 nm,and may be prepared by the conventional hydrothermal method. In thismethod, titanium oxide in its anatase form is used as a startingmaterial. The anatase powder is refluxed with 10 M NaOH solution atapproximately 120° C. for approximately 48 hours. A white mass is thenformed, which is washed with 5% HCl and deionized water untilneutralized. The white powder is then dried at a temperature ofapproximately 110° C. overnight. Titania nanotubes (TNTs) are finallyformed after calcining the dried powder in air at a temperature ofapproximately 450° C. for approximately three hours.

In the following, each catalyst was tested in an electrochemical reactorsystem operated in phase mode. The electrochemical system was similar toa fuel cell test station. Humidified carbon dioxide was fed on thecathode side and 0.5 M NaHCO₃ was used as an analyte on the anode side.Each electrocatalyst sample was dissolved in solvent and painted orcoated on one side of a solid polymer electrolyte (SPE) membrane, viz.,a proton conducting Nafion® 117 membrane (manufactured by E.I. Du PontDo Nemours and Company of Delaware), with 60% Pt—Ru deposited on Vulcan®carbon (manufactured by Vulcan Engineering Ltd. of the United Kingdom)being used as an anode catalyst. Permeation of sodium bicarbonatesolution through the membrane provided the alkalinity required for thereduction reaction to occur. Feeding CO₂ in the gas phase greatlyreduced the mass transfer resistance.

For the first electrocatalyst sample, using pure copper forming 20 wt %of the electrocatalyst, using the experimental reactor described above,at lower voltages (−0.5 V), no hydrocarbon was produced. Maximumfaradaic efficiency (9.6%) for methanol was achieved at −1.5 V. Carbonmonoxide was also produced as a side product. The overall results aregiven below in Table 1:

TABLE 1 Results of reduction of CO₂ over 20% Cu/TNT Faradaic FaradaicFaradaic Efficiency Efficiency Efficiency Potential Current for for forcarbon vs. SCE/V density hydrogen methanol monoxide −0.5 0.4 0 0 0 −1.54.2 6.03 9.6 0.8 −2.5 10.4 74.766 8.4 2.5 −3.5 35.28 86.83 6.3 6.8

For the second electrocatalyst sample, using copper and rutheniumsupported on the titania nanotubes such that the copper forms 20 wt % ofthe electrocatalyst and the ruthenium forms 20 wt % of theelectrocatalyst, using the experimental reactor described above, atlower voltages (−0.5 V), no hydrocarbon was produced. Maximum faradaicefficiency (12.2%) for methanol was achieved at −1.5 V. The overallresults are given below in Table 2:

TABLE 2 Results of reduction of CO₂ over 20% Cu - 20% Ru/TNT FaradaicFaradaic Faradaic Efficiency Efficiency Efficiency Potential Current forfor for carbon vs. SCE/V density hydrogen methanol monoxide −0.5 0.7 0 00 −1.5 6.6 5.3 12.2 2.8 −2.5 14.8 67.2 9.6 7.2 −3.5 39.9 77.4 8.8 13.2

For the third electrocatalyst sample, using copper and iron supported onthe titanic nanotubes such that the copper forms 20 wt % of theelectrocatalyst and the iron forms 20 wt % of the electrocatalyst, usingthe experimental reactor described above, at lower voltages (−0.5 V), nohydrocarbon was produced. The major product was found to be carbondioxide, with no methanol being detected. The overall results are givenbelow in Table 3:

TABLE 3 Results of reduction of CO₂ over 20% Cu - 20% Fe/TNT FaradaicFaradaic Efficiency Efficiency Potential Current for for carbon vs.SCE/V density hydrogen monoxide −0.5 0.34 0 0 −1.5 3.8 14.8 5.4 −2.5 8.478.4 9.4 −3.5 32.2 89.2 8.3

It is to be understood that the present invention is not limited to theembodiments described above, but encompasses any and all embodimentswithin the scope of the following claims.

We claim:
 1. An electrocatalyst for electrochemical conversion of carbondioxide, comprising a copper catalyst material supported on titaniananotubes.
 2. The electrocatalyst as recited in claim 1, wherein thecopper catalyst material comprises pure copper, the pure copper forming20 wt % of the electrocatalyst, the balance being the titania nanotubes.3. The electrocatalyst as recited in claim 1, wherein the coppercatalyst material comprises copper and ruthenium, the copper forming 20wt % of the electrocatalyst, the ruthenium forming 20 wt % of theelectrocatalyst, the balance being the titania nanotubes.
 4. Theelectrocatalyst as recited in claim 1, wherein the copper catalystmaterial comprises copper and iron, the copper forming 20 wt % of theelectrocatalyst, the iron forming 20 wt % of the electrocatalyst, thebalance being the titania nanotubes.
 5. An electrode for electrochemicalconversion of carbon dioxide, comprising a solid polymer electrolytemembrane having an electrocatalyst disposed on one side thereof, theelectrocatalyst having at least one metal supported on titaniananotubes, the at least one metal being selected from the groupconsisting of pure copper, a mixture of copper and ruthenium, and amixture of copper and iron.
 6. A method of making an electrocatalyst forelectrochemical conversion of carbon dioxide, comprising the steps of:dissolving copper nitrate trihydrate in deionized water to form a saltsolution; adding titania nanotubes to the salt solution to form asuspension; heating the suspension; adding a urea solution to thesuspension to form an electrocatalyst in solution, the electrocatalystbeing copper material supported on the titania nanotubes; and removingthe electrocatalyst from the solution.
 7. The method of making anelectrocatalyst as recited in claim 6, further comprising the step ofsonicating the suspension for approximately one hour.
 8. The method ofmaking an electrocatalyst as recited in claim 6, wherein the step ofheating the suspension comprises heating the suspension to a temperatureof approximately 90° C. with stirring.
 9. The method of making anelectrocatalyst as recited in claim 6, further comprising the step ofmaintaining the urea solution and the suspension at a temperature ofapproximately 90° C. for approximately eight hours.
 10. The method ofmaking an electrocatalyst for electrochemical conversion of carbondioxide as recited in claim 6, wherein the step of removing theelectrocatalyst from the solution comprises the steps of: cooling thesolution to room temperature; and centrifuging the solution to separatethe electrocatalyst out of the solution.
 11. The method of making anelectrocatalyst as recited in claim 10, wherein the step of removing theelectrocatalyst from the solution further comprises the steps of washingand drying the electrocatalyst at a temperature of approximately 110° C.12. The method of making an electrocatalyst as recited in claim 11,wherein the step of removing the electrocatalyst from the solutionfurther comprises the step of calcining the washed and driedelectrocatalyst at a temperature of approximately 450° C. forapproximately four hours in an argon gas flow.
 13. The method of makingan electrocatalyst as recited in claim 12, wherein the step of removingthe electrocatalyst from the solution further comprises the step ofreducing the calcined electrocatalyst at a rate of approximately 100mL/min at a temperature of approximately 450° C. for approximately fourhours in a gas flow of approximately 10% hydrogen in argon.
 14. Themethod of making an electrocatalyst for electrochemical conversion ofcarbon dioxide as recited in claim 6, further comprising the step ofdissolving iron nitrate monohydrate in the deionized water to form thesalt solution.
 15. The method of making an electrocatalyst forelectrochemical conversion of carbon dioxide as recited in claim 6,further comprising the step of dissolving ruthenium chloride in thedeionized water to form the salt solution.